Samira Ait Bahadou , Zouhir Mansouri , Ahmed Al-Shami , Hamid Ez-Zahraouy , Omar Mounkachi
{"title":"DFT and AIMD studies of SnFe2O4 as a promising anode for Li-ion batteries","authors":"Samira Ait Bahadou , Zouhir Mansouri , Ahmed Al-Shami , Hamid Ez-Zahraouy , Omar Mounkachi","doi":"10.1016/j.jpcs.2024.112434","DOIUrl":null,"url":null,"abstract":"<div><div>Tin ferrite (SnFe<sub>2</sub>O<sub>4</sub>) is considered as a perspective lithium ion battery anode, owing to its low cost, large theoretical capacity, low toxicity, structural stability, and easy synthesis method. Prior research has been done on the performance of lithium storage in SnFe<sub>2</sub>O<sub>4</sub>. However, the electrochemical processes that take place during the lithiation-delithiation cycle of LIBs have not been explained in depth yet. In order to understand the discharge mechanism in the Li<span><math><msub><mrow></mrow><mrow><mi>x</mi></mrow></msub></math></span>SnFe<sub>2</sub>O<sub>4</sub> anode (x = 0 to 2), we systematically investigated its electrochemical characteristics, structural and electronic properties, average formation energies, open-circuit voltages, diffusion coefficient, and volume expansion using density functional theory. According to our calculations, an increase in Li concentration x up to 1.125 leads to enhanced stability of the Li<span><math><msub><mrow></mrow><mrow><mi>x</mi></mrow></msub></math></span>SnFe<sub>2</sub>O<sub>4</sub> systems. During this process, Li<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span> ions prefer to be intercalated at the octahedral 16c sites, inducing the displacement of Sn<span><math><msup><mrow></mrow><mrow><mn>2</mn><mo>+</mo></mrow></msup></math></span> ions from tetrahedral sites 8a to 16c and 48f sites. However, for 1.125 <span><math><mo><</mo></math></span> x <span><math><mo><</mo></math></span> 2, lithium ions tend to occupy the less stable sites 48f , which reduces the stability of Li<span><math><msub><mrow></mrow><mrow><mi>x</mi></mrow></msub></math></span>SnFe<sub>2</sub>O<sub>4</sub> systems.</div><div>Additionally, the calculated lithium intercalation voltage for full lithiation Li<sub>1.125</sub>SnFe<sub>2</sub>O<sub>4</sub> is equal to 1.5 V, and the distortion of the Li<span><math><msub><mrow></mrow><mrow><mi>x</mi></mrow></msub></math></span>SnFe<sub>2</sub>O<sub>4</sub> system occurs at a voltage of 0.75 V, which is in well agreement with experimental results. The Li-coefficient diffusion on SnFe<sub>2</sub>O<sub>4</sub> at 300 K is calculated by ab initio molecular dynamic simulation and equal to 8.22 × 10<sup>−8</sup> cm<sup>2</sup>/s, which indicates the excellent mobility of Li ions in SnFe<sub>2</sub>O<sub>4</sub>. Considering all these results, we can suggest SnFe<sub>2</sub>O<sub>4</sub> as a promising negative electrode material for lithium-ion batteries.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"198 ","pages":"Article 112434"},"PeriodicalIF":4.3000,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Physics and Chemistry of Solids","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022369724005699","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Tin ferrite (SnFe2O4) is considered as a perspective lithium ion battery anode, owing to its low cost, large theoretical capacity, low toxicity, structural stability, and easy synthesis method. Prior research has been done on the performance of lithium storage in SnFe2O4. However, the electrochemical processes that take place during the lithiation-delithiation cycle of LIBs have not been explained in depth yet. In order to understand the discharge mechanism in the LiSnFe2O4 anode (x = 0 to 2), we systematically investigated its electrochemical characteristics, structural and electronic properties, average formation energies, open-circuit voltages, diffusion coefficient, and volume expansion using density functional theory. According to our calculations, an increase in Li concentration x up to 1.125 leads to enhanced stability of the LiSnFe2O4 systems. During this process, Li ions prefer to be intercalated at the octahedral 16c sites, inducing the displacement of Sn ions from tetrahedral sites 8a to 16c and 48f sites. However, for 1.125 x 2, lithium ions tend to occupy the less stable sites 48f , which reduces the stability of LiSnFe2O4 systems.
Additionally, the calculated lithium intercalation voltage for full lithiation Li1.125SnFe2O4 is equal to 1.5 V, and the distortion of the LiSnFe2O4 system occurs at a voltage of 0.75 V, which is in well agreement with experimental results. The Li-coefficient diffusion on SnFe2O4 at 300 K is calculated by ab initio molecular dynamic simulation and equal to 8.22 × 10−8 cm2/s, which indicates the excellent mobility of Li ions in SnFe2O4. Considering all these results, we can suggest SnFe2O4 as a promising negative electrode material for lithium-ion batteries.
期刊介绍:
The Journal of Physics and Chemistry of Solids is a well-established international medium for publication of archival research in condensed matter and materials sciences. Areas of interest broadly include experimental and theoretical research on electronic, magnetic, spectroscopic and structural properties as well as the statistical mechanics and thermodynamics of materials. The focus is on gaining physical and chemical insight into the properties and potential applications of condensed matter systems.
Within the broad scope of the journal, beyond regular contributions, the editors have identified submissions in the following areas of physics and chemistry of solids to be of special current interest to the journal:
Low-dimensional systems
Exotic states of quantum electron matter including topological phases
Energy conversion and storage
Interfaces, nanoparticles and catalysts.